Oxidative desulfurization of sulfur containing hydrocarbon fuels is a well developed field. See, e.g., pending U.S. patent application Ser. No. 14/987,141, filed Jan. 4, 2016, as well as published U.S. Patent Applications 2013/0028822 and 2013/0026072, all of which are incorporated by reference in their entirety. These materials disclose, inter alia, catalytic compositions which contain 10-50 wt % copper oxide, 5-less than 20 wt % of zinc oxide, and 20-70 w t % aluminum oxide, with X-ray amorphous phases (described infra), having formula CuxZn1-x Al2O4, where X ranges from 0 to 1, and which also contain crystalline ZnO and CuO. These catalysts may be “doped” with one or more promoters, preferably a Group VIB metal oxide such as an oxide of Mo, W, Si, B or P. The promoter may be present in an amount up to 20 wt % of the composition.
These catalytic compositions as well as the compositions of the invention are effective catalysts for selectively oxidizing the organic sulfur compounds in gaseous hydrocarbons preferably at temperatures above 300° C.
Research in the field has shown, however, that catalytic oxidative desulfurization does not perform at a satisfactory level, when prior art catalysts are used by themselves. Hence there is interest in combining catalysts with additives to make them more effective at oxidative desulfurization. One approach is to use zeolites in combination with catalysts. In this respect see, e.g., U.S. Pat. Nos. 4,673,557; 6,579,347; 4,405,443; and 7,749,376, U.S. Patent Publications 2010/0037774 and 2007/0131589, and PCT/NL93/00282, all of which are incorporated by reference in their entirety.
None of these references, however, disclose H-forms of zeolites in combination with catalysts of the type described supra. Such forms of zeolites are disclosed, e.g., by U.S. Pat. Nos. 3,875,290; 3,948,760; and 4,346,067, all of which are incorporated by reference.